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Chung was born in Privett, Hampshire, the daughter of Gillian, a housewife, and Philip Chung, a graphic designer. Her father is of three quarters Chinese descent, while her mother is of English background.[2] Chung attended secondary school at the local Perins School and spent sixth form at Peter Symonds College, Winchester. After school, she chose to pursue modelling .[3]

After becoming a TV personality, Chung made a return to occasional modelling. In 2008, she was the face of Australian fashion label Antipodium's SS 2008 collection and Oxfam's ethical fashion range, Revamped. In September 2008, Chung walked the catwalk as part of the Vivienne Westwood Red Label Spring/Summer 2009 show at London Fashion Week. In early 2009, she became the face of British High Street giant New Look. Chung then joined London-based modelling agency, Select Model Management, and, in April 2009, she modelled Wren's Holiday 2009 collection, alongside her friend Tennessee Thomas. In July 2009, Chung moved to NEXT Model Management and became the face of DKNY Jeans.[7] Chung was the face of South Korean brand MOGG's SS10 campaign. In January 2010, she became the main model of the SS10 Pepe Jeans London campaign and later reprised her role for the FW10 campaign.[8] She was announced as the first celebrity face of Lacoste in June 2010, appearing in both the TV and print advertising campaigns for their "Joy of Pink" fragrance.[9] In January 2011, Chung was announced as the face of Italian sneaker brand Superga, in a campaign to mark their 100th anniversary.[10] In February 2012, she took part in the London Fashion Week show for designer Stella McCartney, where she acted as a guest assistant to magician Hans Klok in a number of illusions including being levitated and sawed in half.[11][12][13]

In April 2006, the then-model Chung was offered the job of co‑host on Popworld on Channel 4, a music show known for its irreverent and awkward style of interviews. Chung and co‑host Alex Zane also presented a weekly radio show called Popworld Radio.[14] The last show aired in July 2007, after Channel 4 decided not to recommission the programme, after nearly seven years.[15] Following this, Chung signed a year-long "golden handcuffs" deal with Channel 4 in August 2007, worth £100,000.[16] As part of this deal, she guest presented Big Brother's Big Mouth and appeared as a panellist on quiz show8 out of 10 Cats. She hosted a number of T4 Movie Specials, 4Music Specials, T4 Holiday Mornings along with T4's coverage of many music festivals.[17]

In January 2008, Chung became one of the four anchor T4 presenters. She hosted T4’s Vanity Lair, a reality show investigating the concept of "beauty". When the show was mentioned in a later interview, "Chung raises her eyebrows, indicating embarrassment".[18] As well as her work on T4, she became a long-time host of Channel 4’s early morning music programme Freshly Squeezed beginning in September 2007. In addition to her Channel 4 commitments, Chung presented the ITV1 series Get a Grip (2007) and BBC Three's The Wall (2008). In mid-2008, Chung began to host more fashion-oriented programming. She was the "roving reporter" on Channel 4's "Gok's Fashion Fix".[19] On the programme, Chung roadtested the latest fashion trends with members of the public, and interviewed fashion designers such as Roberto Cavalli, Karl Lagerfeld, Jean Paul Gaultier, Margherita Missoni and Christian Lacroix. She described it as "pretty much my dream job".[18] Chung also hosted a T4 fashion and music show called Frock Me, with fashion designer Henry Holland.[20] In 2009, Chung was awarded the Elle Style Award for "Best TV Presenter" and Glamour’s award for Best TV Presenter in 2009. Also in 2009, she received Glamour's at the magazine's annual award ceremony.

Chung left Channel 4 and the United Kingdom in April 2009 to pursue a US career. She presented It's On with Alexa Chung for MTV. The live, daily show—billed as TRL's replacement—featured celebrity talk, live music and online interaction with viewers. The show was cancelled in December 2009.[21] She returned to UK TV screens in April 2010 with a second series of Frock Me. In October 2010, she began hosting Gonzo With Alexa Chung, an informal British chat show previously hosted by Zane Lowe, for MTV Rocks.[22] In January 2011, she co‑hosted NBC's "2011 Golden Globe Arrivals Special" with Carson Daly and Natalie Morales. The live show featured interviews with television and film stars as well as segments devoted to fashion on the red carpet.[23] Chung presented the iTunes Festival in July 2011.[24] Chung has since worked on 24 Hour Catwalk, acting as the host and a judge. In 2012, Chung soon became the founding co-host for the nightly music show Fuse News. In December 2013, it was announced that Chung would be leaving Fuse News to focus on other endeavours, leaving new host, Georgie Okell, in her place.[25]

Chung wrote a monthly column for British women's magazine Company from October 2007 to June 2008. She then wrote a weekly newspaper column for Britain'sThe Independent from November 2008 to June 2009, entitled "Girl About Town" and later "New York Doll". In June 2009, she was made a contributing editor of British Vogue and has interviewed designers such as Karl Lagerfeld and Christopher Kane for the publication. Chung's first book, It, was released on 5 September 2013.

Chung is a muse to many fashion designers because of her distinctive personal style.[26] She frequently appears on best-dressed lists, is a regular model for Vogue, Elle and Harper's Bazaar and is often seen in the front row at fashion shows. In 2009, the designer handbag company Mulberry created the "Alexa", a much sought-after bag named after and inspired by her.[27] In January 2010, she was named in Tatler '​s top 10 best-dressed list.[28] In February 2010, Chung collaborated with J.Crew's Madewell on a womenswear line which was unveiled during New York Fashion Week.[29] She collaborated with Madewell for a second collection, released in September 2011.

Vogue '​s Anna Wintour has described Chung as "a phenomenon"[30] while the New York Times has declared her "the Kate Moss of the new generation".[31]Chanel designer Karl Lagerfeld has described her as "beautiful and clever...a modern girl".[32] In December 2010, Bryan Ferry, on behalf of the British Fashion Council, presented Chung with the British Style Award which "recognises an individual who embodies the spirit of British fashion and is an international ambassador for the UK as a leading creative hub for fashion" at a ceremony at the Savoy Theatre in London.[33] At the British Fashion Awards of 2011, 2012 and 2013, Chung won the British Style Award, for which the public voted.[34]

Chung lived with fashion photographer David Titlow, twenty years her senior, for three-and-a-half years until their breakup in 2006.[35] She was in a four-year relationship with Arctic Monkeys frontman Alex Turner from July 2007[36][37] until July 2011,[38] living in both London and New York together. Following their split, Chung purchased a flat in the East Village in New York City.[39][40] Chung has stated that she and Turner remain "best friend(s)."